CN112251751B - Preparation method of 3D-configuration high-bonding-strength sodium titanate nanofiber coating - Google Patents
Preparation method of 3D-configuration high-bonding-strength sodium titanate nanofiber coating Download PDFInfo
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Abstract
The invention discloses a preparation method of a 3D configuration high-bonding strength sodium titanate nanofiber coating, which comprises the steps of taking a pure titanium sheet as a base material, polishing the surface of the pure titanium sheet to be smooth, cleaning and drying the pure titanium sheet for later use; preparing etching liquid, placing the polished titanium sheet into the etching liquid for etching, and then cleaning and drying for later use; soaking the obtained pure titanium sample in a solution with the concentration of 0.5 mol.L‑1～1.0mol·L‑1Carrying out hydrothermal treatment on the titanium surface in the NaOH solution at 220-230 ℃ for 2-17 hours to obtain the high-bonding-strength sodium titanate nanofiber coating on the titanium surface. The invention realizes the construction of three-dimensional nanofiber coatings with different geometric configurations on the surface of the titanium implant by a simple and feasible hydrothermal method, the coatings are uniformly constructed on all surfaces immersed in a solution, dead corners and shielding parts do not exist, and a gradient 3D coating which can be used for manufacturing special bone nails penetrating through cortical bone and cancellous bone can be obtained through the combined action of liquid and gas.
Description
Technical Field
The invention belongs to the technical field of medical metal surface biological activation modification, relates to a preparation technology of a titanium-based medical implant surface bioactive coating, and particularly relates to a preparation method of a 3D configuration high-bonding strength sodium titanate nanofiber coating.
Background
Along with the social and economic development, the civilization progress and the increasing living standard, the human beings pay more attention to the health and medical rehabilitation industry. Meanwhile, the life rhythm is accelerated, the social population is greatly increased, a large number of vehicles are in a rush state, diseases, natural disasters and the like frequently occur, and the number of people suffering from accidental injury is greatly increased. Therefore, the development of biomedical implant materials for reconstruction and repair of human tissues has great economic benefit and great social benefit.
In biomedical metal materials, titanium and titanium alloy have the advantages of strong chemical stability, good corrosion resistance, high specific strength, excellent biocompatibility and the like, and become preferred materials of medical hard tissue implants by virtue of excellent comprehensive properties relative to other metals. At present, titanium metal is a medical metal material with optimal performance in clinic. Therefore, the composite material is more widely applied to the medical fields of orthopedics, orthopedic surgery, dentistry and the like.
Titanium and titanium alloy are biological inert materials, and the biological tissue is regarded as foreign matters in the early stage of implantation, so that a large amount of collagen fibers are generated to wrap the biological inert materials, so that the biological inert materials cannot be firmly combined with bone formation, and clinically, the biological inert materials are shown in the condition that the implant is difficult to achieve biological activity combination with the surrounding bone tissue in a short time. Meanwhile, the elastic modulus of titanium is much higher than that of bone, so that strong chemical osseointegration between titanium alloy and bone is difficult to form, and only mechanical interlocking osseointegration is used instead. In clinical manifestations, the mismatch of mechanical properties between the implant and the bone will result in stress shielding at the implant site, leading to a decrease in bone tissue density near the implant and bone resorption, eventually leading to implant loosening. Therefore, in order to improve the bioactivity of titanium metal and to bond firmly to bone without collagen fiber tissue coating, the surface of titanium metal needs to be modified.
Common surface modification methods include sol-gel, anodic oxidation, micro-arc oxidation, vapor deposition, ion implantation, laser or plasma cladding, and the like. Each modification technology has the characteristics, but the film formation is difficult on the surface of the titanium implant with complex morphology, such as the edge or the hole.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a sodium titanate nanofiber coating with a 3D configuration and high bonding strength, which aims to overcome the existing problems.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a 3D configuration high-bonding-strength sodium titanate nanofiber coating comprises the following steps:
1) mechanical polishing
Adopting a pure titanium sheet as a base material, polishing the surface of the pure titanium sheet to be smooth, cleaning and drying the pure titanium sheet for later use;
2) etching of
Preparing an etching solution, placing the mechanically polished titanium sheet obtained in the step 1) into the etching solution for etching, and then cleaning and drying for later use;
3) hydrothermal treatment
Soaking the pure titanium sample obtained in the step 2) in a solution with the concentration of 0.5 mol.L-1～1.0mol·L-1Carrying out hydrothermal treatment on the titanium surface in the NaOH solution at 220-230 ℃ for 2-17 hours to obtain the high-bonding-strength sodium titanate nanofiber coating on the titanium surface.
Further, in the step 1), metallographic abrasive paper of 100#, 400#, 800# and 1500# is sequentially adopted to polish the surface of the base material.
Further, the cleaning in the step 1) is specifically as follows: and sequentially ultrasonically cleaning the glass substrate by using acetone, absolute ethyl alcohol and deionized water for 10-20 min respectively.
Further, the etching solution in the step 2) is prepared from a nitric acid solution, a hydrofluoric acid solution and deionized water according to a volume ratio of 1: 1: 8, preparing.
Further, the mass fraction of the nitric acid solution is 69.2%; the mass fraction of the hydrofluoric acid solution is 40%.
Further, the etching time in the step 2) is 20-30 s.
Further, the cleaning in the step 2) is specifically as follows: firstly, deionized water is adopted for cleaning for a plurality of times, and then deionized water is adopted for ultrasonic cleaning for 20-30 s.
Further, the step 3) is specifically as follows: injecting the NaOH solution into a hydrothermal reaction kettle, wherein the solution filling degree is 33%, and soaking the pure titanium sample into the solution for hydrothermal treatment.
Compared with the prior art, the invention has the following beneficial technical effects:
1) the invention successfully solves the problems that the film is difficult to form on the surface of the titanium implant with complex appearance, such as the edge or in a hole, and realizes the construction of the nanofiber coating with 3D configuration on the surface of the titanium implant by a simple and feasible hydrothermal method, and the coating is uniformly constructed on each surface immersed in the solution without dead angles and shielding parts;
2) the nanofiber coating prepared by the method has no discontinuous interface with a substrate, and the scratch experiment result shows that the bonding strength of the coating is 31.7 +/-1.9N-49.4 +/-2.3N, and the peeling part is positioned in the coating and is not positioned at the film-substrate bonding part, so that the bonding strength between the coating and the substrate is far greater than the value. The reason for the analysis is as follows:
before hydrothermal treatment, a one-step etching process is arranged, dirt and oxides on the surface of a titanium substrate are further removed by the process, a fresh titanium substrate is fully exposed to react with a hydrothermal solution, the interface is clean and single, and the combination of the substrate and a film layer is increased; and simultaneously, etching to enable the surface of the substrate to present a micro-pit structure, and embedding the coating with the substrate together through the rivet effect, namely, the combination of the substrate and the film layer is increased through mechanical embedding.
Meanwhile, in the sodium hydroxide solution of the hydrothermal reaction, the growth of the sodium titanate nanowire film on the titanium substrate is co-grown upwards and downwards, during the period, a corrosion area appears on the Ti surface, and the sodium titanate nanowires grow downwards to form a dense substrate deep inside. The nanostructure at the initial stage of the reaction is a network skeleton formed by corroding the substrate, and further develops into a leaf shape or a rod shape to a linear shape. Thus, this in situ downward and upward co-growth of sodium titanate nanowires is accompanied. The synergistic effect of the bidirectional co-growth mechanism and the etching mechanism can ensure that the sodium titanate film and the titanium matrix have good bonding strength.
3) The mismatch in mechanical properties between the implant and the bone will result in stress shielding at the implant site, resulting in a decrease in bone tissue density near the implant and bone resorption, ultimately resulting in loosening of the implant. The elastic moduli of the three typical oriented sodium titanate fiber coatings of examples 1-3 of the present invention are 14.53 ± 0.58, 1.69 ± 0.08, and 0.95 ± 0.05GPa, respectively, comparable to the elastic moduli of human cortical and cancellous bone, and are capable of well avoiding the occurrence of stress shielding regions.
4) The gradient 3D coating which can be used for manufacturing the special bone nail penetrating through the cortical bone and the cancellous bone is obtained through the combined action of liquid and gas. According to the elastic modulus gradient coating obtained in the embodiment 6 of the invention, the elastic modulus value of the sample gradually transits from 13.44 +/-0.46 Gpa → 1.97 +/-0.09 Gpa from top to bottom, and the elastic modulus is just in line with the change of the elastic modulus from cortical bone to cancellous bone. The bone nail surface-modified by the method for preparing the gradient coating can be used for penetrating through cortical bone and cancellous bone.
5) The coating has a micro-nano three-dimensional bionic structure shown in figures 1, 4 and 7, so that bone apatite can be quickly induced and formed in a body fluid-like environment, and the biological activity of the implant is improved. The nanofiber structure with high specific surface area enhances the surface wettability with SBF, and the wettability improves water molecules and Na in the SBF2Ti6O13The reaction of the nanofibers results in surface hydroxylation and in turn in the formation of surface Ti-OH groups, which are believed to promote the nucleation of bone apatite. The vertical fibers quasi-vertical to the matrix provide a three-dimensional nano-scale microenvironment, and the ends of the fibers form randomly arranged contact points so as to provide adhesion spots for subsequent cell adhesion; the cellular porous fiber is characterized in that the cellular porous fiber has a multi-layer porous communicating structure, the micron-sized porous structure is implanted into human tissues to be beneficial to the absorption and the transmission of nutrient substances, and the annular porous wall provides enough contact area of adhesive spots for cell adhesion to be beneficial to the cell adhesion; the densely paved nanofibers parallel to the surface of the substrate are very similar to the structure of the natural extracellular matrix, and the natural extracellular matrix is a dense net-shaped structure formed by long fibrous collagen, laminin, fibronectin and proteoglycan which are arranged in a disordered way, so that the paved fiber coating can simulate the extracellular matrix to promote cell adhesion and is beneficial to enhancing the life activity of cells.
6) The hydrothermal solution prepared by the method has simple components, is easy to control, does not contain easily decomposed components, and has stable process; the sodium titanate nanofiber bionic coating is prepared on the surface of pure titanium by a simple and feasible single-step hydrothermal method, the process is simple, and the production cost is low.
Drawings
FIG. 1 is SEM photographs of the surface topography (a) and the cross-sectional topography (b) of a vertical nanofiber structured coating (example 1) prepared using the process of the present invention;
FIG. 2 is a scratch test acoustic emission signal and scratch morphology for a vertical nanofiber coating (example 1 coating) prepared using the process of the present invention: (a) critical load, scratch appearance and acoustic emission signals, (b) microscopic appearance of a stripping part, (c) energy spectrum EDX comparison of a first part and a second part of a surface;
fig. 3 is an SEM topography of the surface of the vertical nanofiber texturing coating (example 1 coating) after SBF soaking for various times: (a) soaking for 14 days, (b) soaking for 18 days, (c) soaking for 22 days;
FIG. 4 is SEM photographs of the surface topography (a) and the cross-sectional topography (b) of a cellular nanofiber-structured coating (example 2) prepared using the process of the present invention;
FIG. 5 is a scratch test acoustic emission signal and scratch morphology for cellular fiber coatings (example 2 coatings) prepared using the process of the present invention: (a) critical load, scratch appearance and acoustic emission signals, (b) microscopic appearance of a stripping part, (c) energy spectrum EDX comparison of a first part and a second part of a surface;
fig. 6 is an SEM topography of the cellular nanofiber patterned coating (example 2 coating) surface after SBF soaking for various times: (a) soaking for 14 days, (b) soaking for 18 days, (c) soaking for 22 days;
FIG. 7 is SEM photographs of surface topography (a) and profile topography (b) of a tiled nanofiber structured coating (example 3) made using the process of the present invention;
fig. 8 is a TEM photograph of a tiled nanofiber prepared using the process of the invention (example 3): (a) bright field images, (b) high resolution and diffraction spots, (c) energy spectrum EDX;
FIG. 9 is a scratch test acoustic emission signal and scratch morphology for a flat-laid nanofiber coating (example 3 coating) prepared using the process of the present invention: (a) critical load, scratch appearance and acoustic emission signals, (b) microscopic appearance of a stripping part, (c) energy spectrum EDX comparison of a first part and a second part of a surface;
fig. 10 is an SEM topography of the surface of the tiled nanofiber structured coating (example 3 coating) after SBF soaking for various times: (a) soaking for 14 days, (b) soaking for 18 days, (c) soaking for 22 days;
FIG. 11 is a SEM image of the surface topography of a nanofiber coating prepared using the process of the present invention (example 6), wherein (a) is a SEM image of the surface topography of a sample below the liquid level and (b) is a SEM image of the surface topography of a sample above the liquid level;
FIG. 12 is SEM pictures of the surface of the sample before and after etching, wherein (a) is the SEM picture of the surface morphology of the sample before etching, and (b) is the SEM picture of the surface morphology of the sample after etching.
Detailed Description
Embodiments of the invention are described in further detail below:
a preparation method of a 3D configuration high-bonding-strength sodium titanate nanofiber coating comprises the following steps:
1) mechanical polishing
The method comprises the steps of using a pure titanium sheet as a base material, polishing the surface of a metal sample by using 100#, 400#, 800# and 1500# metallographic abrasive paper in sequence, then ultrasonically cleaning the metal sample by using acetone, absolute ethyl alcohol and deionized water respectively for 10-20 min in sequence, and drying the metal sample for later use.
2) Etching of
Preparing etching liquid according to the following ratio: hydrofluoric acid solution: the volume ratio of the deionized water is 1: 1: 8, the mass fraction of the nitric acid solution is 69.2%; and the mass fraction of the hydrofluoric acid solution is 40%, the mechanically polished titanium plate is placed into etching solution to be etched for 20-30 s, the titanium plate is cleaned for three times by deionized water, and the titanium plate is ultrasonically cleaned for 20-30 s by the deionized water and is dried for later use.
3) Hydrothermal treatment
The concentration is 0.5 mol.L-1～1.0mol·L-1The NaOH solution is injected into a hydrothermal reaction kettle, the solution filling degree is 33%, a pure titanium sample is soaked into the solution, and the solution is subjected to hydrothermal treatment for 2-17 hours at the temperature of 220-230 ℃, so that the nanofiber coating is obtained on the titanium surface.
The coating has no discontinuous interface with the matrix, has high bonding strength (31.7 +/-1.9N-49.4 +/-2.3N) and elastic modulus (14.53 +/-0.58 GPa-0.95 +/-0.05 GPa) close to that of human bones, can rapidly induce (14d) to generate bone-like apatite in simulated body fluid, and has good biological activity. The hydrothermal solution has the advantages of simple components, easy control, no easily-decomposed components, stable process and low production cost.
The invention realizes the construction of three-dimensional nanofiber coatings with different geometric configurations on the surface of the titanium implant by a simple and feasible hydrothermal method, and the construction of the coatings is uniform and consistent no matter which surface is provided with the coatings, and no dead angle or shielding part exists. Compared with other traditional surface modification methods, in the hydrothermal reaction controlled by the method, the solution under the condition of high temperature and high pressure is in a supercritical state, and the expansion coefficient, the viscosity and the dielectric coefficient of water are correspondingly changed, so that crystal nuclei and crystal grains have higher growth speed than other aqueous solution systems, and therefore, the coating prepared by the hydrothermal method has the characteristics of good and controllable crystal form, high particle purity, good dispersibility, low production cost and the like.
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
Example 1
Firstly, mechanically polishing a titanium sheet, sequentially polishing the surface of the titanium sheet by using 100#, 400#, 800# and 1500# metallographic abrasive paper, and sequentially polishing the surface of the titanium sheet by using acetone and anhydrousAnd (3) ultrasonically cleaning the titanium sheet by using ethanol and deionized water for 20min respectively, and drying the titanium sheet for later use, wherein the surface appearance of the titanium sheet is shown in a figure 12 (a). And (3) placing the mechanically polished titanium sheet into etching liquid for etching for 30s, cleaning for three times by using deionized water, ultrasonically cleaning for 30s by using the deionized water, and drying for later use, wherein the surface appearance of the titanium sheet is shown in fig. 12 (b). The concentration is 1.0 mol.L-1The NaOH solution is injected into a hydrothermal reaction kettle, the solution filling degree is 33 percent, a pure titanium sample treated by the process is soaked into the solution, the solution is subjected to hydrothermal treatment for 2 hours at 220 ℃, the titanium surface is uniformly paved with upright nano fibers which are nearly vertical to the surface of a matrix, the fiber diameter is 33.8 +/-2.5 nm, the coating thickness is about 2.7 mu m, SEM pictures of the surface and section micro-topography are respectively shown in figures 1(a) and (b), discontinuous interfaces do not exist between the coating and the matrix, and the phase is single-phase Na2Ti6O13. The vertical fibers quasi-vertical to the matrix provide a three-dimensional nano-scale microenvironment, and the ends of the fibers form randomly arranged contact points, so that adhesion spots are provided for subsequent cell adhesion. The bond strength of the coating to the titanium substrate was measured using an automatic scratch coating tester, shown in figure 2, comprising: the method comprises the steps of testing acoustic emission signals, critical load, scratch morphology of a coating, an enlarged image of a stripping position and a corresponding energy spectrum of the enlarged image, wherein the critical load corresponding to the stripping position of the coating is 49.4 +/-2.3N. The energy spectrum corresponding to the spalling part shows that the spalling part is positioned in the coating, the measured critical load is the cohesive strength of the coating, and the bonding strength of the coating and the matrix is far larger than the value. The modulus of elasticity of the coating was tested by the nanoindentation method and was found to be 14.53. + -. 0.58 GPa. The bone apatite can be induced to deposit in a simulated body fluid environment for 14 days, and completely covers the surface of the fiber coating at 22 days, so that the bone apatite has good biological activity, and the figure 3 shows that the bone apatite is formed by the surface of the fiber coating.
Example 2
Firstly, mechanically polishing a titanium sheet, grinding the surface of the titanium sheet to be smooth by using metallographic abrasive paper of 100#, 400#, 800# and 1500#, then respectively ultrasonically cleaning the titanium sheet for 15min by using acetone, absolute ethyl alcohol and deionized water in sequence, and drying the titanium sheet for later use. And (3) placing the mechanically polished titanium sheet into an etching solution for etching for 25s, cleaning for three times by using deionized water, ultrasonically cleaning for 25s by using the deionized water, and drying for later use. Will be concentratedDegree of 1.0 mol. L-1The NaOH solution is injected into a hydrothermal reaction kettle, the solution filling degree is 33 percent, a pure titanium sample treated by the process is soaked into the solution, the hydrothermal treatment is carried out for 5 hours at 220 ℃, the diameter and the length of the fiber are increased, the top end of the fiber is bent and gathered into a bundle shape, the length of the bundle fiber is continuously increased, the end part of the fiber is bent and self-assembled to form a multi-layer communicated porous structure shown in the figure, the surface appearance of the sample is a uniform porous cellular shape formed by gathering and surrounding clustered long fibers, the pores are mutually communicated to form a multi-layer three-dimensional structure, the thickness of the cellular porous fiber coating is 8.7 mu m, the diameter of the cellular pores is about 2-10 mu m, the depth is 3-5 mu m, the diameter of the fiber is 37.1 +/-2.8 nm, SEM pictures of the surface and section microscopic appearances of the fiber are respectively referred to 4(a) and (b), and the phase is single-phase Na2Ti6O13. The cellular porous fiber is characterized in that the cellular porous fiber has a multi-layer porous communicating structure, the micron-sized porous structure is implanted into human tissues to be beneficial to the absorption and the transmission of nutrient substances, and the annular porous wall provides enough contact area of adhesive spots for cell adhesion to be beneficial to the cell adhesion. The bond strength of the coating to the titanium substrate was measured using an automatic scratch coating tester, shown in figure 5, comprising: the method comprises the steps of testing acoustic emission signals, critical load, scratch morphology of a coating, an enlarged image of a stripping position and a corresponding energy spectrum of the enlarged image, wherein the critical load corresponding to the stripping position of the coating is 46.5 +/-1.3N. The energy spectrum corresponding to the spalling part shows that the spalling part is positioned in the coating, the measured critical load is the cohesive strength of the coating, and the bonding strength of the coating and the matrix is far larger than the value. The modulus of elasticity of the coating is tested by the nano-indentation method, and the value is 1.69 +/-0.08 GPa. The bone apatite can be induced to deposit in a simulated body fluid environment for 14 days, almost completely covers the surface of the fiber coating at 22 days, and has good biological activity, and the figure 6 shows that the bone apatite has the advantages of high stability, high stability and low cost.
Example 3
Firstly, mechanically polishing a titanium sheet, grinding the surface of the titanium sheet to be smooth by using metallographic abrasive paper of 100#, 400#, 800# and 1500#, then respectively ultrasonically cleaning the titanium sheet for 20min by using acetone, absolute ethyl alcohol and deionized water in sequence, and drying the titanium sheet for later use. Placing the mechanically polished titanium sheet into the notchEtching in the etching solution for 30s, cleaning for three times by using deionized water, ultrasonically cleaning for 30s by using the deionized water, and drying for later use. The concentration is 1.0 mol.L-1The NaOH solution is injected into a hydrothermal reaction kettle, the solution filling degree is 33 percent, a pure titanium sample treated by the process is soaked into the solution, the hydrothermal treatment is carried out for 17 hours at 220 ℃, the fiber length is increased again, the surface of the coating is a compact and novel nanofiber coating which is oriented to be parallel to the surface of the substrate, the fiber diameter is 39.5 +/-2.1 nm, the coating thickness is 13.8 mu m, SEM pictures of the surface and section microscopic appearances of the coating respectively refer to figures 7(a) and (b), TEM pictures of single nanofibers refer to figure 8, the nanofibers at the dotted line circle A in figure 8a are measured, and the electron diffraction pattern (the insert picture at the upper right corner of figure 8b), the high resolution (figure 8b) and the energy spectrum (figure 8c) are analyzed, and the results show that: the nano-fiber is single crystal Na2Ti6O13. The densely paved nanofibers parallel to the surface of the matrix are very similar to the structure of the natural extracellular matrix, and the natural extracellular matrix is a dense net-shaped structure formed by long fibrous collagen, laminin, fibronectin and proteoglycan which are arranged in a disordered way, so that the paved fiber coating can simulate the extracellular matrix to promote cell adhesion and is beneficial to improving the life activity of cells. The bond strength of the coating to the titanium substrate was measured using an automatic scratch coating tester, shown in fig. 9, comprising: the method comprises the steps of testing acoustic emission signals, critical load, scratch morphology of a coating, an enlarged image of a stripping position and a corresponding energy spectrum of the enlarged image, wherein the critical load corresponding to the stripping position of the coating is 31.7 +/-1.9N. The energy spectrum corresponding to the spalling part shows that the spalling part is positioned in the coating, the measured critical load is the cohesive strength of the coating, and the bonding strength of the coating and the matrix is far larger than the value. The modulus of elasticity of the coating was measured by nanoindentation and was found to be 0.95. + -. 0.05 GPa. The bone apatite can be induced to deposit in a simulated body fluid environment for 14 days, and completely covers the surface of the fiber coating at 22 days, so that the bone apatite has good biological activity, and the figure 10 shows that the bone apatite is formed by the surface of the fiber coating.
Example 4
Firstly, mechanically polishing a titanium sheet, sequentially polishing the surface of the titanium sheet by using 100#, 400#, 800# and 1500# metallographic abrasive paper, and sequentially polishing the surface of the titanium sheet by using acetone and anhydrous ethylUltrasonic cleaning with alcohol and deionized water for 10min, and oven drying. And (3) placing the mechanically polished titanium sheet into etching liquid for etching for 20s, cleaning for three times by using deionized water, ultrasonically cleaning for 20s by using the deionized water, and drying for later use. The concentration is 0.5 mol.L-1The NaOH solution is injected into a hydrothermal reaction kettle, the solution filling degree is 33%, the pure titanium sample treated by the process is soaked into the solution, the hydrothermal treatment is carried out for 3 hours at 225 ℃, the surface of the sample is uniformly paved with nano fibers vertical to the surface of the matrix, and the SEM photo of the surface microstructure of the sample is shown in figure 11.
Example 5
Firstly, mechanically polishing a titanium sheet, grinding the surface of the titanium sheet to be smooth by using metallographic abrasive paper of 100#, 400#, 800# and 1500#, then respectively ultrasonically cleaning the titanium sheet for 15min by using acetone, absolute ethyl alcohol and deionized water in sequence, and drying the titanium sheet for later use. And (3) placing the mechanically polished titanium sheet into etching liquid for etching for 30s, cleaning for three times by using deionized water, ultrasonically cleaning for 25s by using the deionized water, and drying for later use. The concentration is 0.8 mol.L-1The NaOH solution is injected into a hydrothermal reaction kettle, the solution filling degree is 33 percent, the pure titanium sample treated by the process is soaked into the solution, the solution is subjected to hydrothermal treatment for 3 hours at 230 ℃, the top ends of the fibers on the surface of the coating lean against each other due to the effects of hydrogen bonds, static electricity and the like, the fibers tend to cluster to form a small cell shape, and the SEM picture of the surface microstructure refers to figure 12.
Example 6
Firstly, mechanically polishing a titanium sheet, grinding the surface of the titanium sheet to be smooth by using metallographic abrasive paper of 100#, 400#, 800# and 1500#, then respectively ultrasonically cleaning the titanium sheet for 20min by using acetone, absolute ethyl alcohol and deionized water in sequence, and drying the titanium sheet for later use. And (3) placing the mechanically polished titanium sheet into etching liquid for etching for 30s, cleaning for three times by using deionized water, ultrasonically cleaning for 25s by using the deionized water, and drying for later use. The concentration is 1.0 mol.L-1The NaOH solution is injected into a hydrothermal reaction kettle, the solution filling degree is 33 percent, a pure titanium sample treated by the process is inserted into the solution, the part below the liquid level accounts for one third, the part above the liquid level accounts for two thirds, the hydrothermal treatment is carried out for 4 hours at the temperature of 220 ℃, and the part immersed into the solution obtains a cellular fiber coating, as shown in figure 11(a), the sample is placed in high-pressure NaOH steam above the liquid level to obtain vertical fibers with slightly gathered tops, as shown in FIG. 11(b), the elastic modulus of the coating is tested by a nanometer pressing method from top to bottom, the value is gradually transited from 13.44 +/-0.46 Gpa → 1.97 +/-0.09 Gpa, and the elastic modulus is a gradient coating which just accords with the change of the elastic modulus from cortical bone to cancellous bone. The bone nail with the surface modified by the method for preparing the gradient coating can be used in the occasions of penetrating through cortical bone and cancellous bone, and the elastic modulus of the contact part of the bone nail and two bones with different elastic modulus is quite equal and cannot generate stress shielding in the using process, so that the density of bone tissues close to the bone nail cannot be reduced, the occurrence of bone absorption is avoided, and the fixing stability of the bone nail is improved. The surface microtopography SEM photograph is shown in figure 11.
Claims (4)
1. A preparation method of a 3D configuration high-bonding-strength sodium titanate nanofiber coating is characterized by comprising the following steps:
1) firstly, mechanically polishing a titanium sheet, polishing the surface of the titanium sheet smoothly by using metallographic abrasive paper of 100#, 400#, 800# and 1500#, sequentially and ultrasonically cleaning the titanium sheet for 20min by using acetone, absolute ethyl alcohol and deionized water respectively, and drying the titanium sheet for later use;
2) placing the mechanically polished titanium sheet into etching liquid for etching for 30s, cleaning for three times by using deionized water, ultrasonically cleaning for 30s by using the deionized water, and drying for later use;
3) the concentration is 1.0 mol.L-1Injecting the NaOH solution into a hydrothermal reaction kettle, wherein the filling degree of the solution is 33 percent, soaking the titanium sheet obtained in the step 2) into the solution, performing hydrothermal treatment for 2 hours at 220 ℃ to form a 3D-configuration high-bonding-strength sodium titanate nanofiber coating, uniformly paving upright nanofibers which are quasi-vertical to the surface of the titanium sheet on the surface of the titanium sheet in the coating, wherein the critical load corresponding to the stripping position of the coating is 49.4 +/-2.3N, the elastic modulus of the coating is 14.53 +/-0.58 GPa, and inducing and depositing bone apatite in a simulated body fluid environment for 14 days, and completely covering the surface of the fiber coating by the bone apatite in 22 days.
2. A preparation method of a 3D configuration high-bonding-strength sodium titanate nanofiber coating is characterized by comprising the following steps:
1) firstly, mechanically polishing a titanium sheet, polishing the surface of the titanium sheet smoothly by using metallographic abrasive paper of 100#, 400#, 800# and 1500#, sequentially and ultrasonically cleaning the titanium sheet for 15min by using acetone, absolute ethyl alcohol and deionized water respectively, and drying the titanium sheet for later use;
2) placing the mechanically polished titanium sheet into etching liquid for etching for 25s, cleaning for three times by using deionized water, ultrasonically cleaning for 25s by using the deionized water, and drying for later use;
3) the concentration is 1.0 mol.L-1Injecting the NaOH solution into a hydrothermal reaction kettle, wherein the filling degree of the solution is 33%, soaking the titanium sheet obtained in the step 2) into the solution, performing hydrothermal treatment for 5 hours at 220 ℃ to obtain a 3D-configuration sodium titanate nanofiber coating with high bonding strength, wherein the surface appearance of the obtained coating is a uniform porous cellular shape formed by gathering and surrounding clustered long fibers, the pores are mutually communicated to form a multi-layer three-dimensional structure, the critical load corresponding to the stripping position of the coating is 46.5 +/-1.3N, the elastic modulus of the coating is 1.69 +/-0.08 GPa, bone apatite is induced and deposited in a simulated body fluid environment for 14 days, and the bone apatite almost completely covers the surface of the fiber coating in 22 days.
3. A preparation method of a 3D configuration high-bonding-strength sodium titanate nanofiber coating is characterized by comprising the following steps:
1) firstly, mechanically polishing a titanium sheet, polishing the surface of the titanium sheet smoothly by using metallographic abrasive paper of 100#, 400#, 800# and 1500#, sequentially and ultrasonically cleaning the titanium sheet for 20min by using acetone, absolute ethyl alcohol and deionized water respectively, and drying the titanium sheet for later use;
2) placing the mechanically polished titanium sheet into etching liquid for etching for 30s, cleaning for three times by using deionized water, ultrasonically cleaning for 30s by using the deionized water, and drying for later use;
3) the concentration is 1.0 mol.L-1Injecting the NaOH solution into a hydrothermal reaction kettle, wherein the solution filling degree is 33 percent, soaking the titanium sheet obtained in the step 2) into the solution, carrying out hydrothermal treatment for 17 hours at 220 ℃ to obtain the 3D-configuration high-bonding-strength sodium titanate nanofiber coating, wherein the surface of the coating is orientedThe critical load of the coating at the stripping position is 31.7 +/-1.9N, the elastic modulus of the coating is 0.95 +/-0.05 Gpa, the bone apatite is induced to be deposited in a simulated body fluid environment for 14 days, and the bone apatite completely covers the surface of the fiber coating at 22 days.
4. A preparation method of a 3D configuration high-bonding-strength sodium titanate nanofiber coating is characterized by comprising the following steps:
1) firstly, mechanically polishing a titanium sheet, polishing the surface of the titanium sheet smoothly by using metallographic abrasive paper of 100#, 400#, 800# and 1500#, sequentially and ultrasonically cleaning the titanium sheet for 20min by using acetone, absolute ethyl alcohol and deionized water respectively, and drying the titanium sheet for later use;
2) placing the mechanically polished titanium sheet into etching liquid for etching for 30s, cleaning for three times by using deionized water, ultrasonically cleaning for 25s by using the deionized water, and drying for later use;
3) the concentration is 1.0 mol.L-1Injecting the NaOH solution into a hydrothermal reaction kettle, wherein the filling degree of the solution is 33%, inserting the titanium sheet obtained in the step 2) into the solution, the part below the liquid surface is one third, and the part above the liquid surface is two thirds, carrying out hydrothermal treatment on the solution at 220 ℃ for 4 hours to obtain the 3D-configuration sodium titanate nanofiber coating with high bonding strength, wherein the elastic modulus of the coating is gradually transited from 13.44 +/-0.46 Gpa → 1.97 +/-0.09 Gpa, and the coating is an elastic modulus gradient coating.
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